Metallizable stilbene triazole azo compounds



Patented Feb. 19, 1946 UNITED STATE PATENT OFFICE METALLIZABLE STIIHBENE TRIAZOL E AZO COMPOUNDS Ernst Keller, Basel, Switzerland, assignor to J. It. Geigy A. G., Basel, Switzerland, a Swissgfirm No Drawing. Application August 31, 1942, Serial No. 456,818. In Switzerland November 5, 1941 13 Claims. (Cl. 260-146) It has been found that new valuable dyestuffs are obtained by condensing amino azo dyestuffs or their copper compounds respectively of the general formula 'wherein W means hydrogen,- a methyl or alkoxy group, X means a hydroxyl or carboxylic group, Y means a hydroxyl, an O.CH2COOH or an alkoxy group, Z1 means hydrogen or a sulionic acid group and Z2 means hydrogen, halogen or the-nitro group, in an alkalinesolution with triazoles of the general formula SOaH $0.11

The two benzene nuclei of the amino azo dyestufi may also be further substituted. For the production of the amino azo dyestuffs according to the above formula the following diazo components may be mentioned: 2-amino-1-hydroxybenzene-4-sulfonic acid, 4-chloro-2-amino-1-hydroxybenzene-fi-sulfonic acid, 4-chloro-2-amino- 1-hydroxybenzene-5-sulfonic acid, 6.-chloro-2- amino-l-hydroxybenzene 4 sulfonic acid, 2- amino-benzoic acid, 5-nitro-2r-aminobenzoic acid,

4-chloro-2-aminophenol, 4--nitro-'-2-amlnophenol, Y

5-nitro-2-aminophenol and the like. As coupling components; use maybe made of: m-aminophenol, m-anisidine, m-ethoxy propyloxyor butoxy-amin'obenzene, 2 -amino 4 hydroxytoluene, 1-amino-2-methyl-5-methoxybenzene, 2:5- dimethoxyaniline, 3-amino-phenoxy acetic acid and many other ones.

The triazoles may still be specially substituted H in the'naphthalene nucleus by sulfonic acid or The manufacture of I carboxylic acid groups. these compounds takes place according to known methods, e. g. by treating coupling products which are obtainable from diazotized 4-nitro-4' aminostilbene-2 2-disulfonic acid with naphthylamine derivatives coupling in o-position w the amino or without pressure. The condensation products can be after-treated with oxidizing or metalyielding agents; moreover, as is known, the copper compounds of the amino azo dyestufis may be brought to condensation. I 1 The present invention will be illustrated hereinafterv by the following examples, the parts being by weight.

Example 1 63.2 parts of the triazole, obtainable by oxidizing the coupling product from diazotized 4-nitro- -4-aminostilbene-2:2'-disulfonic acid and 2- naphthylamine-fi-sulfonic, acid, and'35 parts of tained for instance by treating the dyestuff in 1500 parts of water at 80-90 C. witha solution of 25 parts of crystallized copper sulfate in 100 parts of water and 60 parts of ammonia of 25% strength and stirring this mixture at this temperature for 10 to 12 hours. The metallized compound. is isolated in the usual manner. For metallizing the neutralized solution of the condensation product can be used directly.

"1 The dried metallized dyestuff constitutes a black powder which dissolves in water with an olive coloration, but in concentrated sulfuric acid with a blackish-violet coloration and dyes cellulose fibres in very light-fast, olive shades.

' When the metallized dyestuff is dissolved in 1200 parts of water and 40 parts of caustic soda lye of 36 B. and stirred at 60-70 C. for 2 hours with 150 parts of sodium .hypochlorite (lo-12% active chlorine), a product of similar fastness properties is obtained dyeing cellulose fibre in purer olive shades.

1 'A further similardyestuff is produced by replacing in the above'example the 2-amino-1-hygroup, with oxidation agents, such as chlorine,

sodium hypochlorite, cupric salts and so on.

The condensation is efiected according to the methods known for the production of stilbene dyestuffs'in'the presence of caustic alkalies with droxybenzene-4-sulfonic acid by the 6-chloro-2- amino-1-hydroxybenzene-4-sulfonic acid.

Example 2' 632 parts ofthe triazole described in Example 1 and 38 parts of the copper compound of the amino azo dyestuff from diazotized 2-amino-l-hydroxybenzene-*l-sulfonic acid and m-anisidine are condensed in the usual manner at boiling temperature for to 12 hours with 800 parts of water and 120 parts of caustic soda lye of 36 B. After cooling down the whole is neutralized with hydrochloric acid, until a weak alkaline reaction is reached, and the condensation product is then completely precipitated by means of sodium chloride and filtered.

The dried copper-containing dyestuff is a dark brown powder; it dissolves in water with a reddish-brown coloration, in concentrated sulfuric acid with a blue coloration and dyes cellulose fibres in light-fast reddish brown shades,

If in the above example, instead of the copper compound, the non-metallized amino azo dyestuff is condensed under the same conditions and the condensation product is, for example, converted into the copper compound, as described in Example 1, a similar dyestufi is obtained dyeing cellulose fibres in somewhat more bluish brown shades. I

A further similar dyestufiisobtained, when the triazole described in Example 1 is replaced by the triazole obtainable by the oxidation of the coupling product of the diazotized 4nitro-4'- aminostilbenedisulfonic acid with 2-naphthylamine.

Example 3 63.2 parts of the triazole, described in Example '1, and 22 parts of the amino azo dyestufi from l-hydroxy-Q-amino-4-chloroloenzene and m-anisidine are condensed in the usual'way with 900 parts of water and 300 parts of caustic soda lye of 36 B., e. g. as described in Example 1, and then converted into the copper compound;

The metallized dyestufi constitutes an almost black powder which dissolves in water with a brown coloration, in concentrated sulfuric acid with ablue coloration and dyes cotton in lightfast dark brown shades.

A dyestuif with nearly the same properties-is obtained, when, instead of condensing in an open vessel, the condensation is effected for 8 to 10 hours under reflux-in a pressure vessel at 110"- 120C. and the copper compound, of the dyestufi is produced in the usualmanner.

A further similar dyestufi is produced, when the triazole, described in this example, is replaced by 71 parts of the triazole made by oxidation of the coupling product from diazotized 4-nitro-4- aminostilbene disulfonic acid with 2-naphthylamine-5 7-disulfonic acid.

Example 4 63 parts of the triazole described in Example 1 and the amino azo dyestuff, obtained by coupling 15.4 parts of the diazotized l-hydroxy-Z-amino- 4-nitrobenzene and 12.3 parts of m-anisidine, are condensed under reflux during 14 to 16 hours at boiling temperature with 800 parts of water and 200 parts of caustic soda lye of 36 B. and worked up in the usual manner.

The dyestufi is a brown powder; it dissolves in water with a brown coloration, in concentrated sulfuric acid with blue coloration and dyes cellulose fibres, when after-treated with copper sulfate, in brown-red shades of lightand waterfastness. I

The dyestuif may also be converted in substance into the copper compound; the same dyes cellulose fibres in light-fast brown shades.

Example 5 parts of the triazole, made by oxidation of the coupling product from diazotized 4-nitro-4'- aminostllbene disulfonic acid with Z-aminonaphthalene-B-carboxylic acid, and 35 parts of the amino azo dyestuff, made by coupling diazotized Z-amino-l-hydroxybenzene-4-sulfonic acid with 2:5-dimethoxyaniline, are condensed under reflux at boiling temperature during 14 to 16 hours or in the pressure vessel in 700 parts of water and parts of caustic soda lye of 36 B. and converted into the copper compound in the usual W y- The dried copper compound of the dyestuff constitutes an almost black powder; it dissolves in Water with an olive coloration, in concentrated sulfuric acid with a blackish-violet coloration and dyes cellulose fibres in light-fast olive shades.

In the following table a certain number of further'dyestuffs obtainable according to the present invention is enumerated:

Amino azo dyestufl Coloration of the PPE Diszo component Trim dyeing on cellulose Coupling component fibres -chloro 2-amino-l-hydroxybenzene. 'mtro-2-amino-l-hydroxybcnzcne Z-amino-l-hydroxybenzene-4-sulfonic acid 4-0111Or0-2 amino-1-hydr0xybcnzcne 2:5-dimethoxyaniline. m-aials inc Bronze, Brown.

6-chloro-2-amino-l-hydroxybenzene-i-sulfonic acid D0.

4-11itro-hnminml-hydroxybenzenc 2:5-dimetl1oxyaniline- Bronze 4-chloro-2-amino-l-hydroxybenzene ..do N o. 2 o 4-nitro-2-amino-l-hydroxybonzene 2-ammo-4-hydroxytoluene.. N 0. 2" Yigllgw- 1 Wm G-chloro-2-amino-i-hydroxybenzene-- uifonic acid zzfi-dinrethoxyaniline No. 2-.. Olive. 2 amino-5-nitro-benzoic acid m-an 1sid1ne Brown Anthranilic acid 2-am1i)no-1hydroxybenzene-4-sulfamidc.

0 2:5-dimethoxyanilinc No: 2.--. Bronze 4- 1itro-2-amino-l-hydroxybenzene. 3-an1inophenoxy acetic acid. N0. 2 Yeglowrown 2-amino-1-hydroxybenzene-i-sulfonicacid; 2:5-dimethoxyaniline .i No. 3.... Olive. 6-chlore-2amino-l hydroxybenzene l-sulfonic acid do N o. 3...- o.

4-chloro 2-amino-l-hydroxybenzene 4. 241m 1gnoddiydroxybcnZeneA-suiionic acid i m anisidineun 6-chlor0-2-a!nino 1-hydroxyb euzenel sulionic acid zzs-dimethoxyaniline Supposed formulae of the triazoles No. 1- 6:

No.1 "1 i Nil? CH='OH .N():

N 7 SOIH I 0111 No. 2 l

1?N CH=CH NO:

\l a y N 80:11 O|H No. 3 V

N:IiI CH=CH .NOB xi SOaH SOIH v SOaH Y W No. 4 I

7N 503E H sour No.5 CH=CH NO:

Hons v N SOaH SOzH SOaH CH=CHC NO2 N g V Y SOaH soan Instead of the diazo and coupling components mentioned in the above examples and table, the other compounds enumerated in the general part of this specification can be used quite well for the formation of the monoazo dyestuff.

What I claim is:

1. The copper compound of a dyestuff obtained by condensing in a caustic alkaline medium anamino azo dyestuff of the following general formula Q N M. Z1 I 'wherein X means a member selected from the group consisting of OH and COOH, Y means a member selected from the group consisting of OH, OCH2COOH, and alkoxy groups, ,W means a member selected from the group-consisting of H, CH3 and alkoxy, Z1 means One of H and SO3H and Z2 means one of H, Cl and N02, with a triazole of the following general formula SOgH wherein W means a member selected from the group consisting of H, CH: and alkoxy with a triazole of the following formula CH=CH N09 SOaH SOaH 13,

' 3. The copper compound of a dyestufi obtained by condensing in a caustic alkaline medium an amino azo dyestuff of the following general formula SOzH W wherein W means a member selected from the group consisting of H, CH3 and alkoxy, with a triazole of the following formula 4. The copper compound of a dyestuff obtained by condensing in a caustic alkaline medium the triazole of the formula OOH; I

I 1 TO: L 803K 80311 with the amino azo dyestuff of the formula OH O CH:

N=N NH:

SOaH CH:

5. The copper compound of a dyestufi ob-' tained by condensing in a caustic alkaline medium the triazole of the formula BOaH HOlS

with the amino azo dyestuff of the formula O CH:

6. The copper compound of a dyestufi'obtained by condensing in a caustic alkaline medium the triazole of the formula V fiiQH=cuQNoa S0311 SOaH SOzH v with the amino azo dyestufi of the formula on com I 7. In a process for the manufacture of a copper compound of a metallizable dyestuif, the steps of condensing in a caustic alkaline medium an amino azo dyestuff of the following general wherein X means a member selected from the group consisting of OH and COOH, Y means a member selected from the group consisting of OH, OCHzCOOH and alkoxy groups, W means a member selected from the group consisting of H, CH3 and alkoxy, Z1 means one of H and 303K and Z2 means one of H, Cl and N02, with a triazole of the following general formula S0311 SOaH formula (|)H OCH; an QMQW 1 w wherein W means a member selected from the group consisting of H, CH3 and alkoxy, with a triazole of the following formula TO Q I --N SOaH 'SO H HOBS 7 Q I and after-treating the so-obtained condensation products with a copper-yielding compound.

9. In a process for the manufacture of a copper compound of a metallizabie dyestufl, the steps of condensing in a caustic alkaline medium an amino azo dyestuff of the following general formula (|)H CH:

SOaH W wherein W means a member selected from the group consisting of C, CH3 and alkoxy, with a trlazole of the following formula NqTQ-CI-hCHQNOi N 'SQaH 03H and after-treating the so-obtained condensation products with a copper-yielding compound.

10. In a process for the manufacture of a cop per compound of a metallizable dyestuff, the steps of condensing in a caustic alkaline medium the triazole of the formula N S0311 S0311 with the amino azo dyestufi of the formula and after-treating the so-obtained condensation product with a copper-yielding compound.

11. In a process for the manufacture of a copper compound of a metallizable dyestuff, the steps of condensing in a caustic alkaline medium the triazole of the formula N-NQ0H=0HQ '0: \l' 5 AN 803K I sour HOaS with the amino azo dye-stuff of the formula and. after-treating the so-obtained condensation product with a copper-yielding compound.

12. In a process for the manufactureof a cop per compound of a metallizable dyestuif, the steps of condensing in a caustic alkaline medium the triazole of the formula -N SOaH SOaH SOaH with the amino azo dyestufl of the formula r on OCH; 7 N TQCH=OHQNQ Q =N-NH9 N son: t 5

and after-treating the so-obtained condensation product with a copper-yielding compound.

13. In a process for the manufacture of a copper compound of a metallizable dyestuflz', the step of condensing in a caustic alkaline medium a member selected from the class consisting of an amino azo dyestuff of the formula X Y 4 Z1 1 and a copper compound of the said amino azo dyestuff, with a triazole of the formula wherein the naphthalene nucleus is substituted 

